Herbicidal pyrimidine compounds, compositions containing the same and method of use

ABSTRACT

Herbicidal pyrimidine compound having the formula ##STR1## wherein the substitutents A, R 1 , R 2 , X, Y 1 , Y 2 , Y 3  and Z are as herein below defined.

CROSS-REFERENCE TO RELATED

This is a division of application Ser. No. 07/782,547, filed Oct. 25, 1991, now abandoned, which in turn is a continuation-in-part of application Ser. No. 07/699,392, filed May 14, 1991, now abandoned.

The present invention relates to a novel pyrimidine derivative, a method for producing the same, its use as a herbicide and an intermediate of the same.

European Patent Application No. 0223 406Al, 0249 708Al, 0249 707Al , etc. disclose that pyrimidine derivatives can be used as an active ingredient for herbicides.

However, these compounds are not always said to be satisfactory because they are insufficient in herbicidal activity.

On the other hand, a large number of herbicides for crop lands or non-crop lands are now in use. However, there are many kinds of weeds to be controlled and generation of the weeds extends over a long period of time, so that development of herbicides having a higher herbicidal activity and a broader herbicidal spectrum than before is being desired. Further, in recent years, no-till cultivation has been carried out for the purposes of saving labor, extending cultivation period, preventing soil erosion, etc. Therefore, it is being much desired to develop herbicides having both a high post-emergence herbicidal activity against weeds and pre-emergence herbicidal activity, their excellent residual activity at high level, and a high selectivity to the undesired weeds as compared with the desired crops when crops are cultivated after application of herbicides.

In view of the situation like this, the present inventors have extensively studied, and as a result, have found that pyrimidine derivatives represented by the following formula (1) are compounds having an excellent herbicidal activity and having few foregoing defects, and that some of the derivatives have a high selectivity to the undesired weeds as compared with the desired crops. That is, the pyrimidine derivative can control the undesired weeds widely generated in crop lands or non-crop lands at low dosage rates, has a broad herbicidal spectrum and also can safely be used for no-till cultivation. The present invention is based on this finding.

According to the present invention, there are provided a pyrimidine derivative having the formula (hereinafter present compound), ##STR2## wherein A is C₃ -C₆ oxacycloalkyl, C₃ -C₆ oxacycloalkyl substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl and halogen, C₂ -C₆ oxacycloalkyl C₁ -C₆ alkyl, C₂ -C₆ oxacycloalkyl C₁ -C₆ alkyl substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl and halogen, C₃ -C₅ dioxacycloalkyl, C₃ -C₅ dioxacycloalkyl substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl and halogen, C₃ -C₅ dioxacycloalkyl C₁ -C₆ or C₃ -C₅ dioxacycloalkyl C₁ -C₆ alkyl substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl and halogen;

each of R¹ and R², which may be the same or different, is C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkoxy or halogen;

X is oxygen or sulfur;

Z is nitrogen or CY⁴ ;

each of Y¹, Y² and Y³, which may be the same or different, is hydrogen, halogen, C₁ -C₆ alkyl or C₁ -C₆ alkoxy; and

Y⁴ is hydrogen, hydroxyl, mercapto, nitro, halogen, C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆ alkynyl, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy, halo C₁ -C₆ alkyl, halo C₂ -C₆ alkenyl, halo C₂ -C₆ alkynyl, halo C₁ -C₆ alkoxy, halo C₃ -C₆ alkenyloxy, halo C₃ -C₆ alkynyloxy, C₁ -C₆ alkoxy C₁ -C₆ alkyl, C₃ -C₆ alkenyloxy C₁ -C₆ alkyl, C₃ -C₆ alkynyloxy C₁ -C₆ alkyl, cyano, formyl, carboxyl, C₁ -C₆ alkoxycarbonyl, C₃ -C₆ alkenyloxycarbonyl, C₃ -C₆ alkynyloxycarbonyl, phenyl, phenyl substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen, phenoxy, phenoxy substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen, phenylthio, phenylthio substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen, benzyloxy, benzyloxy substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen, benzylthio, benzylthio substituted with at least one member selected from the group consisting of C₁ -C.sub. 6 alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen, ##STR3## wherein each of R⁵ and R⁶, which may be the same or different, is hydrogen, C₁ -C₆ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl, ##STR4## wherein R⁵ and R⁶ are as defined above, ##STR5## wherein R⁷ is C₁ -C₆ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl and m is an integer of 0, 1 or 2, ##STR6## wherein X¹ is oxygen or sulfur, and R⁷ is as defined above, or ##STR7## wherein R⁷ and m are as defined above, and n is an integer of from 1 to 4;

a method for producing the pyrimidine derivative (1) which comprises reacting a compound having the formula, ##STR8## wherein A, X, Z, Y¹, Y² and Y³ are as defined above, with a compound having the formula, ##STR9## wherein each of R¹ and R² are as defined above; W is halogen or ##STR10## wherein R⁸ is C₁ -C₆ alkyl, benzyl or benzyl substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halogen or nitro; and l is an integer of 0, 1 or 2; a method for producing the pyrimidine derivative (1) which comprises the steps of

(i) reacting a carboxylic acid derivative having the formula (4), ##STR11## wherein X, Z, Y¹, Y², Y³, R¹ and R² are as defined above, with an acid-halogenating agent or an active esterifying agent to obtain a reaction product; and

(ii) reacting the reaction product with an alcohol derivative having the formula,

    HO--A                                                      (5)

wherein A is as defined above;

a method for producing the pyrimidine derivative (1) which comprises reacting a carboxylic acid derivative having the formula (4), ##STR12## wherein X, Z, Y¹, Y², Y³, R¹ and R² are as defined above, with a halide having the formula,

    W.sup.3 --A                                                (7)

wherein A is as defined above, and W³ is halogen; a compound having the formula, ##STR13## wherein A, X, Z, Y¹, Y² and Y³ are as defined above; a herbicidal composition which comprises as an active ingredient a herbicidally effective amount of the pyrimidine derivative described above, and an inert carrier or a diluent;

a method for controlling undesirable weeds, which comprises applying the above herbicidal composition to an area where undesirable weeds grow or are likely to grow; and

a use of the pyrimidine derivative as a herbicide.

In the formula [1], examples of the C₁ -C₆ alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, etc; examples of the C₁ -C₆ alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, hexyloxy, etc; and examples of the C₁ -C₆ alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, hexyloxycarbonyl, etc.

The halogen atom in the formula [1] includes fluorine, chlorine, bromine and iodine.

When a substituted or unsubstituted C₂ -C₆ oxacycloalkyl C₁ -C₆ alkyl group is selected as A, the examples thereof include oxacyclobutylmethyl, oxacyclobutylethyl, oxacyclobutylpropyl, oxacyclobutylpentyl, oxacyclobutylhexyl, oxacyclopentylmethyl, oxacyclopentylethyl, oxacyclopentylpropyl, oxacyclopentylpentyl, oxacyclopentylhexyl, oxacyclohexylmethyl, oxacyclohexylethyl, oxacyclohexylbutyl, oxacyclohexylpentyl, oxacyclohexylhexyl, oxacycloheptylmethyl, oxacycloheptylethyl, oxacycloheptylbutyl, oxacycloheptylpentyl, oxacycloheptylhexyl, methyloxacyclobutylmethyl, dimethyloxacyclobutylethyl, ethyloxacyclobutylpropyl, hexyloxacyclobutylbutyl, chlorooxacyclobutylpentyl, dichlorooxacyclobutylhexyl, difluorooxacyclopentylmethyl, bromooxacyclopentylethyl, oxacyclopropylmethyl, oxacyclopropylhexyl, etc.

When a substituted or unsubstituted C₃ -C₅ dioxacycloalkyl group is selected as A, the examples thereof include dioxacyclopentyl, dioxacyclohexyl, dioxacycloheptyl, methyldioxacyclopentyl, dimethyldioxacyclohexyl, chlorodioxacycloheptyl group, etc.

When a substituted or unsubstituted C₃ -C₅ dioxacycloalkyl C₁ -C₆ alkyl group is selected as A, the examples thereof include dioxacyclopentylmethyl, dioxacyclopentylethyl, dioxacyclopentylbutyl, dioxacyclopentylpentyl, dioxacyclopentylhexyl, dioxacyclohexylmethyl, dioxacyclohexylethyl, dioxacyclohexylpropyl, dioxacyclohexylpentyl, dioxacyclohexylhexyl, dioxacycloheptylmethyl, dioxacycloheptylethyl, dioxacycloheptylpropyl, dioxacycloheptylpentyl, dioxacycloheptylhexyl, methyldioxacyclopentylmethyl, dimethyldioxacyclohexylmethyl, ethyldioxacycloheptylmethyl, hexyldioxacyclopentylethyl, chlorodioxacyclohexylethyl, dichlorodioxacycloheptylethyl, difluorodioxacyclopentylpropyl, bromodioxacyclohexylpropyl, etc.

When a substitited or unsubstituted C₃ -C₆ oxacycloalkyl group is selected as A, the examples thereof include oxacyclobutyl, oxacyclopentyl, oxacyclohexyl, oxacycloheptyl, methyloxacyclobutyl, dimethyloxacyclopentyl, dichlorooxacyclohexyl, etc.

When a halo C₁ -C₆ alkoxy group is selected as R¹ or R², the examples thereof include fluoromethoxy, difluoromethoxy, trifluoromethoxy, etc.

When a C₂ -C₆ alkenyl group is selected as Y⁴, the examples thereof include vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 2-hexenyl, etc.

When a C₂ -C₆ alkynyl group is selected as Y⁴, the examples thereof include ethynyl, propargyl, 1-butynyl, 2-butynyl, 2-pentynyl, 3-pentynyl, 2-hexynyl, etc.

When a C₃ -C₆ alkenyloxy group is selected as Y⁴, the examples thereof include allyloxy, 2-butenyloxy, 3-butenyloxy, 2-hexenyloxy, etc.

When a C₃ -C₆ alkynyloxy group is selected as Y⁴, the examples thereof include propargyloxy, 2-butynyloxy, 3-butynyloxy, 2-hexynyloxy, etc.

When a halo C₁ -C₆ alkyl group is selected as Y⁴, the examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, 2-chloroethyl, 3-bromopropyl, etc.

When a halo C₂ -C₆ alkenyl group is selected as Y⁴, the examples thereof include 1-chlorovinyl, 3-chloroallyl, 5-bromo-2-pentenyl, 6-iodo-2-hexenyl, 5,5,5-trifluoro-2-pentenyl, etc.

When a halo C₂ -C₆ alkynyl group is selected as Y⁴, the examples thereof include 2-iodoethynyl, 5-bromo-2-pentynyl, 6-iode-2-hexynyl, 5,5,5-trifluoro-2-pentynyl, etc.

When a halo C₁ -C₆ alkoxy group is selected as Y⁴, the examples thereof include fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1,1,2,2-tetra-fluoroethoxy, etc.

When a halo C₃ -C₆ alkenyloxy group is selected as Y⁴, the examples thereof include 3-chloroallyloxy, 5-bromo-2-pentenyloxy, 6-iodo-2-hexenyloxy, 5,5,5-trifluoro-2-pentenyloxy, etc.

When a halo C₃ -C₆ alkynyloxy group is selected as Y⁴, the examples thereof include 5-bromo-2-pentynyloxy, 5-chloro-2-pentynyloxy, 3-iodopropargyloxy, etc.

When a C₁ -C₆ alkoxy C₁ -C₆ alkyl group is selected as Y⁴, the examples thereof include methoxymethyl, ethoxymethyl, 2-methoxyethyl, 4-n-propoxybutyl, 2-n-butoxyethyl, 6-hexyloxyhexyl, etc.

When a C₃ -C₆ alkenyloxy C₁ -C₆ alkyl group is selected as Y⁴, the examples thereof include allyloxymethyl, 2-allyloxyethyl, 4-allyloxybutyl, 3-(2-butenyloxy)propyl, 6-(hexenyloxy)hexyl, etc.

When a C₃ -C₆ alkynyloxy C₁ -C₆ alkyl group is selected as Y⁴, the examples thereof include propargyloxymethyl, 2-propargyloxyethyl, 4-propargyloxybutyl, 3-(2-butynyloxy)propyl, 6-(2-hexenyloxy)hexyl, etc.

When a C₃ -C₆ alkenyloxycarbonyl group is selected as Y⁴, the examples thereof include allyloxycarbonyl, 2-butynyloxycarbonyl, 3-butynyloxycarbonyl, 2-hexenyloxycarbonyl, etc.

When a C₃ -C₆ alkynyloxycarbonyl group is selected as Y⁴, the examples thereof include propargyloxycarbonyl, 2-butynyloxycarbonyl, 3-butynyloxycarbonyl, 2-hexynyloxycarbonyl, etc.

When a substituted phenoxy group is selected as Y⁴, the examples thereof include 2-methylphenoxy, 3-ethylphenoxy, 4-hexylphenoxy, 2,6-dimethylphenoxy, 3-methoxyphenoxy, 4-isopropoxyphenoxy, 3-hexyloxyphenoxy, 2-trifluoromethylphenoxy, 3-difluoromethylphenoxy, 2-methoxycarbonylphenoxy, 2-ethoxycarbonylphenoxy, 2-n-propoxycarbonylphenoxy, 2-hexyloxycarbonylphenoxy, 2-fluorophenoxy, 2-chlorophenoxy, 3-bromophenoxy, 2,4-dichlorophenoxy, etc.

When a substituted phenyl group is selected as Y⁴, the examples thereof include 2-methylphenyl, 3-ethylphenyl, 4-hexylphenyl, 2,6-dimethylphenyl, 3-methoxyphenyl, 4-isopropoxyphenyl, 3-hexyloxyphenyl, 2-trifluoromethylphenyl, 3-difluoromethylphenyl, 2-methoxycarbonylphenyl, 2-ethoxycarbonylphenyl, 2-n-propoxycarbonylphenyl, 2-hexyloxycarbonylphenyl, 2-fluorophenyl, 2-chlorophenyl, 3-bromophenyl, 2,4-dichlorophenyl, etc.

When a substituted phenylthio group is selected as Y⁴, the examples thereof include 2-methylphenylthio, 3-ethylphenylthio, 4-hexylphenylthio, 2,6-dimethylphenylthio, 3-methoxyphenylthio, 4-isopropoxyphenylthio, 3-hexyloxyphenylthio, 2-trifluoromethylphenylthio, 3-difluoromethylphenylthio, 2-methoxycarbonylphenylthio, 2-ethoxycarbonylphenylthio, 2-n-propoxycarbonylphenylthio, 2-hexyloxycarbonylphenylthio, 2-fluorophenylthio, 2-chlorophenylthio, 3-bromophenylthio, 2,4-dichlorophenylthio, etc.

When a substituted benzyloxy group is selectd as Y⁴, the examples thereof include 2-methylbenzyloxy, 3-ethylbenzyloxy, 4-hexylbenzyloxy, 2,6-dimethylbenzyl-oxy, 3-methoxybenzyloxy, 4-isopropoxybenzyloxy, 3-hexyloxybenzyloxy, 2-trifluoromethylbenzyloxy, 3-difluoromethylbenzyloxy, 2-methoxycarbonylbenzyloxy, 2-ethoxycarbonylbenzyloxy, 2-n-propoxycarbonylbenzyloxy, 2-hexyloxycarbonylbenzyloxy 2-fluorobenzyloxy, 2-chlorobenzyloxy, 3-bromobenzyloxy, 2,4-dichlorobenzyloxy, etc.

When a substituted benzylthio group is selected as Y⁴, the examples thereof include 2-methylbenzylthio, 3-ethylbenzylthio, 4-hexylbenzylthio, 2,6-dimethylbenzylthio, 3-methoxybenzylthio, 4-isopropoxybenzylthio, 3-hexyloxybenzylthio, 2-trifluoromethylbenzylthio, 3-difluoromethylbenzylthio, 2-methoxycarbonylbenzylthio, 2-ethoxycarbonylbenzylthio, 2-n-propoxycarbonylbenzylthio, 2-hexyloxycarbonylbenzylthio, 2-fluorobenzylthio, 2-chlorobenzylthio, 3-bromobenzylthio, 2,4-dichlorobenzylthio, etc.

When a C₃ -C₆ alkenyl group is selected as R⁵, R⁶ or R⁷, the examples thereof include allyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 2-hexenyl, etc.

When a C₃ -C₆ alkynyl group is selected as R⁵, R⁶ or R⁷, the examples thereof include propargyl, 1-butynyl, 2-butynyl, 2-pentynyl, 3-pentynyl, 2-hexynyl, etc.

In the compound of the formula (I), the substituents R¹ and R², which may be the same or different, are preferably C₁ -C₆ alkoxy, and more preferably, both of them are methoxy.

A is preferably a C₃ -C₅ dioxacycloalkyl C₁ -C₆ alkyl group. More preferably, A is 1,3-dioxolane-2-yl C₁ -C₆ alkyl group or 1,3-dioxan-2-yl C₁ -C₆ alkyl group. Most preferably, A is 1,3-dioxolane-2-yl ethyl group or 1,3-dioxan-2-yl ethyl group.

X is preferably oxygen.

Z is preferably nitrogen or CY⁵ wherein Y⁵ is hydrogen or halogen, a halo C₁ -C₆ alkyl group, a C₁ -C₆ alkyl group, a C₁ -C₆ alkoxy group or a substituted or unsubstituted phenyl group. More preferably, Z is nitrogen or CY⁵ in which Y⁵ is hydrogen or halogen.

Y¹ and Y², which may be the same or different, are preferably a hydrogen atom or a fluorine atom.

Y³ is preferably hydrogen, fluorine or a C₁ -C₆ alkoxy group. Specific examples of the pyrimidine derivative of the present invention include

2-(1,3-dioxan-2-yl)ethyl 2-(4,6-dimethoxypyrimidin-2-yl)oxybenzoate, ##STR14## 2-(1,3-dioxan-2-yl)ethyl 2-chloro-6-(4,6-dimethoxypyrimidin-2-yl)oxybenzoate, ##STR15## and 2-(1,3-dioxan-2-yl)ethyl 3-(4,6-dimethoxypyrimidin-2-yl)oxypicolinate, ##STR16##

A method for producing the present compound is as follows.

The present compound (1) can be produced by reacting a compound represented by the formula (2), ##STR17## wherein A, X, Y¹, Y², Y³ and Z are as defined above, with a compound represented by the formula (3), ##STR18## wherein R¹, R² and W are as defined above.

This reaction is usually carried out with or without a solvent in the presence of a base. The reaction temperature usually ranges from room temperature to the boiling point of the solvent, and the reaction time usually ranges from 10 minutes to 24 hours. Referring to the amounts of the reagents used for this reaction, the amount of the compound (3) is usually 1.0 to 1.5 equivalents based on 1 equivalent of the compound (2), and that of the base is usually 1.0 to 5.0 equivalents based on the same. The solvent includes aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benezene, toluene, xylene), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene), ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone), alcohols (e.g. methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol, methyl cellosolve, diethylene glycol, glycerin), esters (e.g. ethyl formate, ethyl acetate, butyl acetate), nitro compounds (e.g. nitroethane, nitrobenzene), nitriles (e.g. acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine), acid amides (e.g. formamide, N,N-dimethylformamide, acetamide), sulfur compounds (e.g. dimethyl sulfoxide, sulfolane), liquid ammonia, water and the mixtures thereof.

Specific examples of the base are organic bases (e.g. pyridine, triethylamine, N,N-diethylaniline), inorganic bases (e.g. sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride), alkali metal alkoxides (e.g. sodium methoxide, sodium ethoxide), etc.

After completion of the reaction, the reaction solution may be after-treated as usual. That is, water is added to the solution which is then extracted with an organic solvent and concentrated, and if necessary, the product obtained is subjected to chromatography, distillation, recrystallization, etc. Thus, the desired present compound can be obtained.

The compound represented by the formula (3) can be produced according to Japanese Patent Application Kokai No. 63-23870, J. Org. Chem., 26, 792 (1961), etc.

The present compound can also be produced by reacting a compound represented by the formula (4), ##STR19## wherein R¹, R², X, Y¹, Y², Y³ and Z are as defined above, with an acid-halogenating agent or an active esterifying agent (hereinafter reaction (i)), and reacting the resulting reaction product with an alcohol derivative represented by the formula (5),

    HO--A                                                      (5)

wherein A is as defined above (hereinafter reaction (ii).

In the above reaction (i), specific examples of the acid-halogenating agent are thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosgene, oxalic acid dichloride, etc. Specific examples of the active esterifying agent are N,N'-disubstituted carbodiimides such as N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, etc.; arylsulfonyl chlorides such as 2,4,6-trimethylbenzenesulfonyl chloride, 2,4,6-triisopropylbenzenesulfonyl chloride, etc.; N,N'-carbonyldiimidazole; diphenylphosphorylazide; N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline; N-ethyl-2'-hydroxybenzisoxazolium trifluoroborate; N-ethyl-5-phenylisoxazolium-3'-sulfonate; etc.

By this reaction, a compound represented by the formula (6), ##STR20## wherein R¹, R², X, Y¹, Y² , Y³ and Z are as defined above, is produced in the reaction system.

In the above formula (6), a substituent W² represents a halogen atom when the acid-halogenating agent was used; W² represents an N,N'-disubstituted-2-isoureido group when N,N'-disubstituted carbodiimide was used as the active esterifying agent; W² represents an arylsulfonyloxy group when arylsulfonyl chloride was used as said agent; W² represents an imidazolyl group when N,N'-carbonyldiimidazole was used as said agent; W² represents an azide group when diphenylphosphorylazide was used as said agent; W² represents an ethoxycarbonyloxy group when N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline was used as said agent; W² represents a 3-(N-ethylaminocarbonyl)-2-hydroxyphenoxy group when N-ethyl-2'-hydroxybenzisoxazolium trifluoroborate was used as said agent; and W² represents a group ##STR21## when N-ethyl-5-phenylisoxazolium-3'-sulfonate was used as said agent.

In the reaction system, W² can also take a form of acid anhydride containing the moiety represented by the formula, ##STR22## wherein R¹, R², X, Y¹, Y², Y³ and Z are as defined above.

The amount of the foregoing acid-halogenating agent or active esterifying agent used is usually 1 to 10 equivalents based on 1 equivalent of the compound represented by the formula (4).

The amount of the alcohol derivative of the formula (5) used is usually 1 to 5 equivalents based on 1 equivalent of the compound represented by the formula (4).

The reactions (i) and (ii) can also be carried out, if necessary, in the presence of a base. Such a base includes organic bases (e.g. 1 -methylimidazole, 3 -nitro-1H-1,2,4-triazole, 1H-tetrazole, 1H-1,2,4-triazole, imidazole, pyridine, triethylamine) and inorganic bases (e.g. potassium carbonate). The amount of the base used is usually 1 to 20 equivalents based on 1 equivalent of the compound represented by the formula (4).

The reactions (i) and (ii) are usually carried out in the presence of an inert solvent. Such a solvent includes aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene), ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol diemthyl ether), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone), esters (e.g. ethyl formate, ethyl acetate, butyl acetate), nitro compounds (e.g. nitroethane, nitrobenzene), nitriles (e.g. acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine), acid amides (e.g N,N-dimethylformamide), sulfur compounds (e.g. dimethyl sulfoxide, sulfolane) and the mixtures thereof.

Generally, the reaction temperature usually ranges from 0° C. to the boiling point of the solvent in any of the reactions (i) and (ii). The reaction time usually ranges from 1 to 24 hours for each reaction, and from about 1 to about 48 hours through the reactions (i) and (ii).

After completion of the reaction, the reaction solution may be after-treated as usual. That is, water is added to the solution which is then extracted with an organic solvent and concentrated, and if necessary, the product obtained is subjected to the chromatography, distillation, recrystallization, etc. Thus, the desired present compound can be obtained.

The present compound can also be prepared by reacting a compound represented by the formula (4), with a halide represented by the formula (7)

    W.sup.3 --A                                                (7)

wherein A and W³ are as defined above.

This reaction is usually carried out with or without a solvent in the presence of a base. The reaction temperature usually ranges from room temperature to the boiling point of the solvent, and the reaction time usually ranges from 30 minutes to 24 hours. Referring to the amounts of the reagents used for this reaction, the amount of the halide (7) is usually 1.0 to 5.0 equivalents based on 1 equivalent of the compound (4), and that of the base is usually 1.0 to 5.0 equivalents based on the same. Examples of the solvent include aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene), ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol direthyl ether) and ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone), esters (e.g. ethyl formate, ethyl acetate, butyl acetate), nitro compounds (e.g. nitroethane, nitrobenzene), nitriles (e.g. acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine), acid amides (e.g. formamide, N,N-dimethylformamide, acetamide), sulfur compounds (e.g. dimethyl sulfoxide, sulfolane), and mixtures thereof.

The base includes organic bases (e.g. pyridine, triethylamine, N,N-diethylaniline), inorganic bases (e.g. sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride), alkali metal alkoxides (e.g. sodium methoxide, sodium ethoxide), etc.

After completion of the reaction, the reaction solution is after-treated as usual. That is, water is added to the solution which is then extracted with an organic solvent and concentrated, and if necessary, the product obtained is subjected to chromatography, distillation, recrystallization, etc. Thus, the desired present compound can be obtained.

The compound represented by the formula (4) can be produced according to EP 0 223 406 Al, etc.

In producing the present compounds, when the compound (a starting material for compound (1)), represented by the formula (2) is other than the compounds in which Y⁴ is a group, ##STR23## in which R⁶ is as defined above, or a group, ##STR24## in which R⁶ is as defined above, said compound can be produced as follows: The method comprises reacting an aromatic carboxylic acid halide represented by the following formula (8), ##STR25## wherein X, Y¹, Y² and Y³ are as defined above, W⁴ represents a halogen atom, R⁹ represents a C₁ -C₆ alkyl group, and Z¹ represents CY^(4') wherein Y^(4') is hydrogen, nitro, halogen, C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₂ -C₆ alkynyl, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy, halo C₁ -C₆ alkyl, halo C₂ -C₆ alkenyl, halo C₂ -C₆ alkynyl, halo C₁ -C₆ alkoxy, halo C₃ -C₆ alkenyloxy, halo C₃ -C₆ alkynyloxy, C₁ -C₆ alkoxy C₁ -C₆ alkyl, C₃ -C₆ alkenyloxy C₁ -C₆ alkyl, C₃ -C₆ alkynyloxy C₁ -C₆ alkyl, cyano, formyl, carboxyl, C₁ -C₆ alkoxycarbonyl, C₃ -C₆ alkenyloxycarbonyl, C₃ -C₆ alkynyloxycarbonyl, phenyl, phenyl substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen, phenoxy, phenoxy substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen, phenylthio, phenylthio substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen, benzyloxy, benzyloxy substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen, benzylthio, benzylthio substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen, ##STR26## wherein each of R^(5') and R^(6'), which may be the same or different, is C₁ -C₆ alkyl, C₃ -C₆ alkenyl or C₃ -C₆ alkynyl, ##STR27## wherein R^(5') and R^(6') are as defined above, ##STR28## wherein R⁷ and m are as defined above, ##STR29## wherein R⁷ and X¹ are as defined above, or ##STR30## wherein R⁷, m and n are as defined above, or a group represented by the formula, ##STR31## in which R⁹ and X are as defined above, with the alcohol derivative represented by the formula (5) in the presence of a dehydrohalogenating agent and hydrolyzing the resulting compound with a base (e.g. sodium hydroxide, potassium hydroxide) or an acid (e.g. hydrochloric acid, sulfuric acid) to remove the group, ##STR32##

or alternatively, the method comprises reacting a compound represented by the formula, ##STR33## wherein X, Y¹, Y², Y³, Z¹ and R⁹ are as defined above, with the compound (7),

    W.sup.3 --A                                                (7)

in the presence of a dehydrohalogenating agent and hydrolyzing the resulting compound with a base (e.g. sodium hydroxide, potassium hydroxide) or an acid (e.g. hydrochloric acid, sulfuric acid) to remove the group, ##STR34##

Specific examples of the dehydrohalogenating agent are pyridine, triethylamine, N,N-diethylaniline, etc.

After completion of the reaction, the reaction solution may be after-treated as usual. That is, water is added to the solution which is then extracted with an organic solvent and concentrated, and if necessary, the product obtained is subjected to the chromatography, distillation, recrystallization, etc. Thus, the compound (2) can be obtained.

The compound represented by the formula (2) can be produced by reacting an aromatic carboxylic acid derivative represented by the formula (9), ##STR35## wherein X, Y¹, Y², Y³ and Z are as defined above, with an acid-halogenating agent or an active esterifying agent (hereinafter reaction (iii), and reacting the resulting reaction product with the alcohol derivative represented by the formula (5) (hereinafter reaction (iv)).

The above reactions (iii) and (iv) can be carried out according to the foregoing reactions (i) and (ii), respectively. The aromatic carboxylic acid halide derivative (8) can be produced according to Beilstein H10/p.86, EI10/p.43, EII10/p.55, EIII10/p.151, EIV10/p.169, etc.

The aromatic carboxylic acid derivative (9) can be produced according to J. Org. Chem., 27, 3551 (1962), Chem. Pharm. Bull., 31, 407 (1983), Yakugaku Zasshi, 99, 657 (1979), Chem. Pharm. Bull., 27, 1468 (1979), J. Med. Chem., 21, 1093 (1978), Yakugaku Zasshi, 92, 1386 (1972), Eur. J. Med. Chem-Chim. Ther., 21, 379 (1986), J. Chem. Soc., Perkin Trans. 1, 2069 (1979), J. Chem. Soc., Perkin Trans. 1, 2079 (1979), J. Chem. Soc., Chem. Commun., 1127 (1968), J. Med. Chem., 31, 1039 (1988), Indian J. Chem., 25B, 796 (1984), J. Am. Chem. Soc., 107, 4593 (1985), J. Org. Chem., 50, 718 (1985), J. Agric. Food Chem., 32, 747 (1984), J. Pharm. Pharmacol., 35, 718 (1983), J. Org. Chem., 48, 1935 (1983), J. Chem. Soc., Chem. Commun., 1974, 362, etc.

Compound (1) and Compound (2) include their stereo isomers having a herbicidal activity.

The present compounds (1) have an excellent herbicidal activity and some of them have an excellent selectivity to the undesired weeds as compared with the desired crops.

That is, the present compound, when used for foliar treatment and soil treatment in upland fields, exhibits a herbicidal activity against a wide variety of undesired weeds. Also, the present compound (1), when used for flooding treatment in paddy fields, exhibits a herbicidal activity against a wide variety of undesired weeds.

The present compound (1) can control a wide range of weeds generated in crop lands or non-crop lands, can be applied in low dosage rates, has a broad herbicidal spectrum and also can safely be used for notill cultivation in soybean fields, peanut fields, corn fields, etc.

As weeds which can be controlled by the present compound, there are mentioned for example broadleaved weeds such as wild buckwheat (Polygonum convolvulus), pale smartweed (Polygonum lapathifolium), common purslane (Portulaca oleracea), chickweed (Stellaria media), common lambsquarters (Chenopodium album), redroot pigweed (Amaranthus retroflexus), radish (Raphanus sativus), wild mustard (Sinapis arvensis), shepherds purse (Capsella bursa-pastoris), hemp sesbania (sesbania exaltata), sicklepod (Cassia obtusifolia), velvetleaf (Abutilon theophrasti), prickly sida (Sida spinosa), field pansy (Viola arvensis), cleavers (Galium aparine), ivyleaf morningglory (Ipomoea hederacea), tall morningglory (Ipomoea purpurea), field bindweed (Convolvulus arvensis), red deadnettle (Lamium purpureum), henbit (Lamium amplexicaure), jimsonweed (Datura stramonium), black nightshade (Solanum nigrum), birdseye speedwell (Veronica persica), cocklebur (Xanthium strumarium), sunflower (Helianthus annuus), scentless chamomile (Matricaria perforata), corn marigold (Chrysanthemum segetum), etc.; Gramineae weeds such as Japanese millet (Echinochloa frumentacea), barnyardgrass (Echinochloa crus-galli), green foxtail (Setaria viridis), giant foxtail (Setaria faberi), large crabgrass (Digitaria sanguinalis), annual bluegrass (Poa annua), blackgrass (Alopecurus myosuroides), oat (Avena sativa), wild oat (Avena fatua), johnsongrass (Sorghum halapense), quackgrass (Agropyron repens), downy brome (Bromus tectorum), bermudagrass (Cynodon dactylon), etc.; Commelinaceae weeds such as dayflower (Commelina communis), etc.; and Cyperaceae weeds such as rice flatsedge (Cyperus iria), purple nutsedge (Cyperus rotundus), etc. In addition, the present compounds give such no phytotoxicity as becoming a problem to main crops such as corn, wheat, barley, rice, soybean, cotton, beet, etc.

In flooding treatment in paddy fields, the present compounds exhibit a herbicidal activity against gramineous weeds such as barnyardgrass (Echinochloa oryzicola), etc.; broad-leaved weeds such as false pimpernel (Lindernia procumbens), indian toothcup (Rotala indica), waterwort (Elatine triandra), Ammannia multiflora, etc.; Cyperaceae weeds such as smallflower umbrellaplant (Cyperus difformis), bulrush (Scirpus juncoides), slender spikerush (Eleocharis acicularis), water nutgrass (Cyperus serotinus), etc.; monochoria (Monochoria vaginalis), arrowhead (Sagittaria pygmaea), etc.

When the present compound (1) is used as an active ingredient for herbicides, it is usually formulated before use into emulsifiable concentrates, wettable powders, suspension formulations, granules, water-dispersible granules, etc. by mixing the present compound (1) with solid carriers, liquid carriers, surface active agents or other auxiliaries for formulation.

The content of the compound (1) as an active ingredient in these preparations is normally within a range of about 0.001 to 90% by weight, preferably of about 0.003 to 80% by weight.

Examples of the solid carriers are fine powders or granules of kaolin clay, attapulgite clay, bentonite, terra alba, pyrophyllite, talc, diatomaceous earth, calcite, walnut shell powders, urea, ammonium sulfate and synthetic hydrated silicon dioxide, etc.

Examples of the liquid carriers are aromatic hydrocarbons (e.g. xylene, methylnaphthalene), alcohols (e.g. isopropanol, ethylene glycol, cellosolve), ketones (e.g. acetone, cyclohexanone, isophorone), vegetable oils (soybean oil, cotton seed oil), dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, water, etc.

Examples of the surface active agents used for emulsification, dispersion or spreading, etc. are anionic surface active agents such as salts of alkyl sulfates, alkylsulfonates, alkylarylsulfonates, dialkyl sulfosuccinates, salts of polyoxyethylene alkylaryl ether phosphoric acid esters, etc., and nonionic surface active agents such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc.

Examples of the other auxiliaries for formulation are lignosulfonates, aliginates, polyvinyl alcohol, gum arabic CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), etc.

The present compound (1) is usually formulated into an appropriate formulation and used in soil treatment, foliar treatment or flooding treatment before or after emergence of weeds. The soil treatment includes soil surface treatment and soil incorporation treatment. The foliar treatment includes, in addition to the treatments of plants mentioned above, direct treatment in which the formulation is applied only to weeds so as to prevent the formulation from adhering to crops.

The herbicidal activity of the present compound (1) can be expected to be increased by using the compound in mixture with other herbicides. Further, the present compound (1) can also be used in mixture with insecticides, acaricides, nematocides, fungicides, plant growth regulators, fertilizers, soil improvers, etc.

The present compound (1) can be used as an active ingredient for herbicides used in paddy fields, ridges of paddy fields, plowed fields, fields other than plowed fields, orchards, pastures, turfs, forests and fields other than agricultural fields, etc.

When the present compound (1) is used as an active ingredient for herbicides, the dosage rate varies depending upon the weather conditions, preparation forms, when, how and where the treatment is carried out, weeds species to be controlled, crops species to be protected, etc. Usually, however, the dosage rate is from 0.003 grams to 100 grams of the active ingredient per are, preferably from 0.01 grams to 50 grams of the active ingredient per are.

The herbicidal composition of the invention formulated in the form of an emulsifiable concentrate, a wettable powder or a suspension formulations may ordinarily be employed after diluting it with water at a volume of about 1 to 10 liters per are. If necessary, auxiliaries such as a spreading agent are added to the water. The granules are usually applied as they are without being diluted.

Examples of the spreading agent are, in addition to the foregoing surface active agents, substances such as polyoxyethylene resin acids (esters), lignosulfonates, abietates, dinaphthylmethanedisulfonates, paraffin, etc.

The present invention will be illustrated in more detail with reference to the following production examples, formulation examples and test examples, which are not however to be interpreted as limiting the invention thereto.

First, production examples for the present compound (1) are shown.

PRODUCTION EXAMPLE 1

0.84 Gram of 2-(1,3-dioxan-2-yl)ethyl salicylate and 0.73 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine was dissolved in 10 ml of N,N-dimethylformamide, and 0.51 g of anhydrous potassium carbonate was added thereto. The resulting solution was stirred at 100° to 110° C. for 1 hour. The reaction solution was allowed to cool, poured into diluted hydrochloric acid, and extracted with ethyl acetate. The organic layer separated from the aqueous layer was washed with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to silica gel column chromatography (mfd. by Merck & Co., Inc., solvent: chloroform) to obtain 0.50 g of 2-(1,3-dioxan-2-yl)ethyl 2-(4,6-dimethoxypyrimidin-2-yl)oxybenzoate [present compound (V-1)].

¹ H-NMR (CDCl₃) δ: 1.28-2.23 (m, 4H), 3.61-4.45 (m, 7H), 3.75 (s, 6H), 5.71 (s, 1H), 7.07-8.04 (m, 4H).

PRODUCTION EXAMPLE 2

10 Milliliters of N,N-dimethylformamide in which 0.22 g of 60% sodium hydride in oil has been suspended was mixed with 5 ml of N,N-dimethylformamide solution of 1.38 g of 2-(4,6-dimethoxypyrimidin-2-yl)oxy benzoic acid. After stirring the mixture at room temperature for 30 minutes, 10 ml of N,N-dimethylformamide solution of 1.81 g of 2-(2-bromoethyl)-1,3-dioxolane was added thereto. The resulting solution was stirred at 100° to 110° C. for 2 hours. The reaction solution was allowed to cool, poured into diluted hydrochloric acid, and extracted with ethyl acetate. The organic layer separated from the aqueous layer was washed with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to silica gel column chromatography (mfd. by Merck & Co., Inc., solvent: chloroform) to obtain 1.20 g of 2-(1,3-dioxolan-2-yl)ethyl 2-(4,6-dimethoxypyrimidin-2-yl)oxybenzoate [present compound (V-2)].

¹ H-NMR (CDCl₃) δ: 1.71-2.31 (m, 2H), 3.68-3.93 (m, 4H), 3.73 (s, 6H), 4.21 (t, 2H, J=6.4 Hz), 4.79 (t, 1H, J=5.0 Hz), 5.67 (s, 1H), 7.08-7.98 (m, 4H).

PRODUCTION EXAMPLE 3

0.55 Gram of 2-(4,6-dimethoxypyrimidin-2-yl)oxybenzoic acid, 0.21 g of tetrahydrofuryl alcohol and 0.85 g of 2,4,6-triisopropylbenzenesulfonyl chloride were dissolved in 5 ml of tetrahydrofuran. Subsequently, 0.45 g of 1-methylimidazole was added to the mixture. After stirring the resulting solution at room temperature for 1 hour in order to carry out the reaction, the reaction solution was poured into diluted hydrochloric acid, and exracted with ethyl acetate. The organic layer separated from the aqueous layer was washed with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was subjected to silica gel column chromatography (mfd. by Merch & Co., Inc., solvent: chloroform) to obtain 0.30 g of tetrahydrofurfuryl 2-(4,6-dimethoxypyrimidin-2-yl)oxybenzoate [present compound (III-9)].

¹ H-NMR (CDCl₃) δ: 1.45-2.15 (m, 4H), 3.65-4.20 (m, 5H), 3.76 (s, 6H), 5.73 (s, 1H), 7.12-8.10 (m, 4H).

PRODUCTION EXAMPLE 4

According to the procedure shown in Production Example 2, 2-(1,3-dioxan-2-yl)ethyl 6-fluoro-2-(4,6-dimethoxypyrimidin-2-yl)oxybenzoate (present compound (V-24)) can be obtained by reacting 2.94 g of 2-fluoro-6-(4,6-dimethoxypyrimidin-2-yl)oxybenzoic acid, 0.44 g of sodium hydride in oil and 5.85 g of 2-(bromoethyl)-1,3-dioxane.

PRODUCTION EXAMPLE 5

According to the procedure shown in Production Example 2, 2-(1,3-dioxan-2-yl)ethyl 2-(4,6-dimethoxy-pyrimidin-2-yl)oxy-6-phenylbenzoate (present compound (V-49)) can be obtained by reacting 3.52 g of 2-(4,6-dimethoxypyrimidin-2-yl)oxy-6-phenylbenzoic acid, 0.44 g of sodium hydride in oil and 5.85 g of 2-(bromoethyl)-1,3-dioxane.

PRODUCTION EXAMPLE 6

According to the procedure shown in Production Example 2, 2-(1,3-dioxan-2-yl)ethyl 6-methoxy-2-(4,6-dimethoxypyrimidin-2-yl)oxybenzoate (present compound (V-31)) can be obtained by reacting 3.06 g of 2-methoxy-6-(4,6-dimethoxypyrimidin-2-yl)oxybenzoic acid, 0.44 g of sodium hydride in oil and 5.85 g of 2-(bromoethyl)-1,3-dioxane.

PRODUCTION EXAMPLE 7

According to the procedure shown in Production Example 2, 2-(1,3-dioxan-2-yl)ethyl 2-(4,6-dimethoxypyrimidin-2-yl)oxy-6-methylbenzoate (present compound (V-34) can be obtained by reacting 2.94 g of 2-(4,6-dimethoxypyrimidin-2-yl)oxy-6-methylbenzoic acid, 0.44 g of sodium hydride in oil and 5.85 g of 2-(bromoethyl)-1,3-dioxane.

PRODUCTION EXAMPLE 8

According to the procedure shown in Production Example 2, 2-(1,3-dioxan-2-yl)ethyl 2-(4,6-dimethoxypyrimidin-2-yl)oxy-6-trifluoromethylbenzoate (present compound (V-33)) can be obtained by reacting 2.94 g of 2-(4,6-dimethoxypyrimidin-2-yl)oxy-6-trifluoromethylbenzoic acid 0.44 g of sodium hydride in oil and 5.85 g of 2-(bromoethyl)-1,3-dioxane.

Table 1 illustrates specific examples of the compound (1), which can be produced by using the corresponding starting compounds. Compounds (V-2), (V-10), (V-14) to (V-23) were prepared according to the procedure of Production Example 2. Compounds (II-3), (V-4), (III-5), (III-7), (V-8), (IV-11), and (III-9) were prepared according to the procedure of Production Example 3.

                                      TABLE 1                                      __________________________________________________________________________      ##STR36##                                                                                                                          Physical properties       Compound                                             (m.p.,                    No.   A              Y.sup.1                                                                           Y.sup.2                                                                           Y.sup.3                                                                            X  Z          R.sup.1                                                                            R.sup.2                                                                            refractive                __________________________________________________________________________                                                          index)                    (II-1)                                                                                ##STR37##     H  H  H   O  CF         OCH.sub.3                                                                          OCH.sub.3                     (II-2)                                                                                ##STR38##     H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (II-3)                                                                                ##STR39##     H  H  H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.24                                                                 1.5355                    (II-4)                                                                                ##STR40##     H  H  H   S  CCl        OCH.sub.3                                                                          OCH.sub.3                     (II-5)                                                                                ##STR41##     H  H  H   O  CBr        OCH.sub.3                                                                          OCH.sub.3                     (II-6)                                                                                ##STR42##     H  H  H   S  CBr        OCH.sub.3                                                                          OCH.sub.3                     (II-7)                                                                                ##STR43##     H  H  H   O  COCH.sub.3 OCH.sub.3                                                                          OCH.sub.3                     (II-8)                                                                                ##STR44##     H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (II-9)                                                                                ##STR45##     H  H  H   O  CCl        CH.sub.3                                                                           OCH.sub.3                     (II-10)                                                                               ##STR46##     H  H  H   O  CF         Cl  OCH.sub.3                     (II-11)                                                                               ##STR47##     H  H  H   O  N          Cl  Cl                            (I-12)                                                                                ##STR48##     H  H  H   O  CCF.sub.3  OCH.sub.3                                                                          OCH.sub.3                     (II-13)                                                                               ##STR49##     H  H  H   O  CCH.sub.3  OCH.sub. 3                                                                         OCH.sub.3                     (II-14)                                                                               ##STR50##     H  H  H   O  CC.sub.6 H.sub.5                                                                          OCH.sub.3                                                                          OCH.sub.3                     (II-15)                                                                               ##STR51##     H  H  H   O  CNO.sub.2  OCH.sub.3                                                                          OCH.sub.3                     (II-16)                                                                               ##STR52##     H  H  F   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (III-1)                                                                               ##STR53##     H  H  H   O  N          OCH.sub.3                                                                          OCH.sub.3                     (III-2)                                                                               ##STR54##     H  H  H   O  CF         OCH.sub.3                                                                          OCH.sub.3                     (III-3)                                                                               ##STR55##     H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (III-4)                                                                               ##STR56##     H  H  H   S  CCl        OCH.sub.3                                                                          OCH.sub.3                     (III-5)                                                                               ##STR57##     H  H  H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.22.5                                                               1.5391                    (III-6)                                                                               ##STR58##     H  H  H   S  CBr        OCH.sub.3                                                                          OCH.sub.3                     (III-7)                                                                               ##STR59##     H  H  H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.22.5                                                               1.5335                    (III-8)                                                                               ##STR60##     H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (III-9)                                                                               ##STR61##     H  H  H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.25                                                                 1.5332                    (III-10)                                                                              ##STR62##     H  H  H   O  CCF.sub.3  OCH.sub.3                                                                          OCH.sub.3                     (III-11)                                                                              ##STR63##     H  H  H   O  CSCH.sub.3 OCH.sub.3                                                                          OCH.sub.3                     (III-12)                                                                              ##STR64##     H  H  H   O  CC.sub.2 H.sub.5                                                                          OCH.sub.3                                                                          OCH.sub.3                     (III-13)                                                                              ##STR65##     H  H  H   O  CCN        OCH.sub.3                                                                          OCH.sub.3                     (III-14)                                                                              ##STR66##     H  H  H   O  CNO.sub.2  OCH.sub.3                                                                          OCH.sub. 3                    (III-15)                                                                              ##STR67##     H  H  H   O  COCH.sub.3 OCH.sub.3                                                                          OCH.sub.3                     (III-16)                                                                              ##STR68##     H  H  H   O  COH        OCH.sub.3                                                                          OCH.sub.3                     (IV-1)                                                                                ##STR69##     H  H  H   O  N          OCH.sub.3                                                                          OCH.sub.3                     (IV-2)                                                                                ##STR70##     Cl H  H   O  CF         OCH.sub.3                                                                          OCH.sub.3                     (IV-3)                                                                                ##STR71##     H  CH.sub.3                                                                          H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (IV-4)                                                                                ##STR72##     H  H  OCH.sub.3                                                                          S  CCl        OCH.sub.3                                                                          OCH.sub.3                     (IV-5)                                                                                ##STR73##     H  H  F   O  CBr        OCH.sub.3                                                                          OCH.sub.3                     (IV-6)                                                                                ##STR74##     C.sub.2 H.sub.5                                                                   H  H   S  CBr        OCH.sub.3                                                                          OCH.sub.3                     (IV-7)                                                                                ##STR75##     H  Cl H   O  COCH.sub.3 OCH.sub.3                                                                          OCH.sub.3                     (IV-8)                                                                                ##STR76##     H  H  F   O  CCF.sub.3  OCH.sub.3                                                                          OCH.sub.3                     (IV-9)                                                                                ##STR77##     H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (IV-10)                                                                               ##STR78##     H  H  H   O  CF         OCH.sub.3                                                                          OCH.sub.3                     (IV-11)                                                                               ##STR79##     H  H  H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          m.p. 118-119°                                                           C.                        (IV-12)                                                                               ##STR80##     H  H  H   S  CCl        OCH.sub.3                                                                          OCH.sub.3                     (IV-13)                                                                               ##STR81##     H  H  H   O  CBr        OCH.sub.3                                                                          OCH.sub.3                     (IV-14)                                                                               ##STR82##     H  H  H   S  CBr        OCH.sub.3                                                                          OCH.sub.3                     (IV-15)                                                                               ##STR83##     H  H  H   O  COCH.sub.3 OCH.sub.3                                                                          OCH.sub.3                     (IV-16)                                                                               ##STR84##     H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (V-1)                                                                                 ##STR85##     H  H  H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.24                                                                 1.5341                    (V-2)                                                                                 ##STR86##     H  H  H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.22                                                                 1.5325                    (V-3)                                                                                 ##STR87##     H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (V-4)                                                                                 ##STR88##     H  H  H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.24                                                                 1.5249                    (V-5)                                                                                 ##STR89##     H  H  H   O  CBr        OCH.sub.3                                                                          OCH.sub.3                     (V-6)                                                                                 ##STR90##     H  H  H   S  CBr        OCH.sub.3                                                                          OCH.sub.3                     (V-7)                                                                                 ##STR91##     H  H  H   O  COCH.sub.3 OCH.sub.3                                                                          OCH.sub.3                     (V-8)                                                                                 ##STR92##     H  H  H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.21.5                                                               1.5408                    (V-9)                                                                                 ##STR93##     CH.sub.3                                                                          H  H   O  CH         OCH.sub.3                                                                          OCH.sub.3                     (V-10)                                                                                ##STR94##     H  H  H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.22                                                                 1.5367                    (V-11)                                                                                ##STR95##     H  H  F   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (V-12)                                                                                ##STR96##     H  H  OCH.sub.3                                                                          O  CH         OCH.sub.3                                                                          OCH.sub.3                     (V-13)                                                                                ##STR97##     H  H  F   O  CH         OCH.sub.3                                                                          OCH.sub.3                     (V-14)                                                                                ##STR98##     H  Cl H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          m.p. 71-72°                                                             C.                        (V-15)                                                                                ##STR99##     H  CH.sub.3                                                                          H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          m.p. 67-68°                                                             C.                        (V-16)                                                                                ##STR100##    H  Cl H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.24                                                                 1.5285                    (V-17)                                                                                ##STR101##    H  CH.sub.3                                                                          H   O  CH         OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.24                                                                 1.5215                    (V-18)                                                                                ##STR102##    H  H  H   O  CH         CH.sub.3                                                                           CH.sub.3                                                                           n.sub.D.sup.24                                                                 1.5419                    (V-19)                                                                                ##STR103##    H  H  H   O  CH         Cl  OCH.sub.3                                                                          n.sub.D.sup.24                                                                 1.5375                    (V-20)                                                                                ##STR104##    H  H  H   O  N          OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.24                                                                 1.5193                    (V-21)                                                                                ##STR105##    H  H  H   O  N          OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.24                                                                 1.5055                    (V-22)                                                                                ##STR106##    H  H  H   O  N          OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.24                                                                 1.5190                    (V-23)                                                                                ##STR107##    H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                                                                          n.sub.D.sup.24                                                                 1.5243                    (V-24)                                                                                ##STR108##    H  H  H   O  F          OCH.sub.3                                                                          OCH.sub.3                     (V-25)                                                                                ##STR109##    H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (V-26)                                                                                ##STR110##    H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (V-27)                                                                                ##STR111##    H  H  F   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (V-28)                                                                                ##STR112##    H  H  OCH.sub.3                                                                          O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (V-29)                                                                                ##STR113##    H  H  H   O  CBr        OCH.sub.3                                                                          OCH.sub.3                     (V-30)                                                                                ##STR114##    H  H  H   S  CBr        OCH.sub.3                                                                          OCH.sub.3                     (V-31)                                                                                ##STR115##    H  H  H   O  COCH.sub.3 OCH.sub.3                                                                          OCH.sub.3                     (V-32)                                                                                ##STR116##    H  H  H   S  CCl        OCH.sub.3                                                                          OCH.sub.3                     (V-33)                                                                                ##STR117##    H  H  H   O  CCF.sub.3  OCH.sub.3                                                                          OCH.sub.3                     (V-34)                                                                                ##STR118##    H  H  H   O  CCH.sub.3  OCH.sub.3                                                                          OCH.sub.3                     (V-35)                                                                                ##STR119##    H  H  H   O  CNO.sub.2  OCH.sub.3                                                                          OCH.sub.3                     (V-36)                                                                                ##STR120##    H  H  H   O  CNH.sub.2  OCH.sub.3                                                                          OCH.sub.3                     (V-37)                                                                                ##STR121##    H  H  H   O  CCN        OCH.sub.3                                                                          OCH.sub.3                     (V-38)                                                                                ##STR122##    H  H  H   O  CC.sub.2 H.sub.5                                                                          OCH.sub.3                                                                          OCH.sub.3                     (V-39)                                                                                ##STR123##    H  H  H   O  COH        OCH.sub.3                                                                          OCH.sub.3                     (V-40)                                                                                ##STR124##    H  H  H   O  CSCH.sub.3 OCH.sub.3                                                                          OCH.sub.3                     (V-41)                                                                                ##STR125##    H  H  H   O  CCOOCH.sub.3                                                                              OCH.sub.3                                                                          OCH.sub.3                     (V-42)                                                                                ##STR126##    H  H  H   O  CCON(CH.sub.3).sub.2                                                                      OCH.sub.3                                                                          OCH.sub.3                     (V-43)                                                                                ##STR127##    H  H  H   O  COC.sub.3 H.sub.7 (i)                                                                     OCH.sub.3                                                                          OCH.sub.3                     (V-44)                                                                                ##STR128##    H  H  H   O  CC.sub.4 H.sub.9 (n)                                                                      OCH.sub.3                                                                          OCH.sub.3                     (V-45)                                                                                ##STR129##    H  H  H   O  COCF.sub.2 CHF.sub.2                                                                      OCH.sub.3                                                                          OCH.sub.3                     (V-46)                                                                                ##STR130##    H  H  H   O  CSC.sub.5 H.sub.11                                                                        OCH.sub.3                                                                          OCH.sub.3                     (V-47)                                                                                ##STR131##    H  H  H   O  CSOC.sub.2 H.sub.5                                                                        OCH.sub.3                                                                          OCH.sub.3                     (V-48)                                                                                ##STR132##    H  H  H   O  CSO.sub.2 CH.sub.3                                                                        OCH.sub.3                                                                          OCH.sub.3                     (V-49)                                                                                ##STR133##    H  H  H   O                                                                                  ##STR134##                                                                               OCH.sub.3                                                                          OCH.sub.3                     (V-50)                                                                                ##STR135##    H  H  H   O                                                                                  ##STR136##                                                                               OCH.sub.3                                                                          OCH.sub.3                     (V-51)                                                                                ##STR137##    H  H  H   O                                                                                  ##STR138##                                                                               OCH.sub.3                                                                          OCH.sub.3                     (V-52)                                                                                ##STR139##    H  H  H   O                                                                                  ##STR140##                                                                               OCH.sub.3                                                                          OCH.sub.3                     (V-53)                                                                                ##STR141##    H  H  H   O                                                                                  ##STR142##                                                                               OCH.sub.3                                                                          OCH.sub.3                     (V-54)                                                                                ##STR143##    H  H  H   O                                                                                  ##STR144##                                                                               OCH.sub.3                                                                          OCH.sub.3                     (V-55)                                                                                ##STR145##    H  H  H   O                                                                                  ##STR146##                                                                               OCH.sub.3                                                                          OCH.sub.3                     (V-56)                                                                                ##STR147##    H  H  H   O                                                                                  ##STR148##                                                                               OCH.sub.3                                                                          OCH.sub.3                     (V-57)                                                                                ##STR149##    H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (V-58)                                                                                ##STR150##    H  H  H   O  CF         OCH.sub.3                                                                          OCH.sub.3                     (V-59)                                                                                ##STR151##    H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     (V-60)                                                                                ##STR152##    H  H  H   S  CCl        OCH.sub.3                                                                          OCH.sub.3                     (V-61)                                                                                ##STR153##    H  H  H   O  CBr        OCH.sub.3                                                                          OCH.sub.3                     (V-62)                                                                                ##STR154##    H  H  H   S  CBr        OCH.sub.3                                                                          OCH.sub.3                     (V-63)                                                                                ##STR155##    H  H  H   O  COCH.sub.3 OCH.sub.3                                                                          OCH.sub.3                     (V-64)                                                                                ##STR156##    H  H  H   O  CCl        OCH.sub.3                                                                          OCH.sub.3                     __________________________________________________________________________

Production Examples for the compound (2), a starting material, are shown below.

PRODUCTION EXAMPLE 9

9.00 Grams of acetylsalycilic acid and 9.95 g of 2-(2-bromoethyl)-1,3-dioxane were dissolved in 100 ml of N,N-dimethylformaide was mixed with 7.60 g of anhydrous potassium carbonate. The resulting solution was stirred at 120° C. to 130° C. for 3 hours. The reaction solution was poured into diluted hydrochloric acid, and extracted with ethyl acetate. The organic layer separated from the aqueous layer was washed with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the residue obtained was distilled under reduced pressure to obtain 10.5 g of 2-(1,3-dioxan-2-yl)ethyl salycilate in a yield of 83%.

b.p.: 120° C.-122° C./0.07 mmHg,

n_(D) ²⁴ 1.5246.

Table 2 illustrates specific examples of the compound (2), which can be produced by using the corresponding starting materials.

                                      TABLE 2                                      __________________________________________________________________________      ##STR157##                                                                    A               Y.sup.1                                                                           Y.sup.2                                                                           Y.sup.3                                                                            X Z                                                  __________________________________________________________________________      ##STR158##     H  H  H   O CF                                                  ##STR159##     H  H  H   O CCl                                                 ##STR160##     H  H  H   O CH                                                  ##STR161##     H  H  H   S CCl                                                 ##STR162##     H  H  H   O CBr                                                 ##STR163##     H  H  H   S CBr                                                 ##STR164##     H  H  H   O COCH.sub.3                                          ##STR165##     H  H  H   O CCl                                                 ##STR166##     H  H  H   O CCl                                                 ##STR167##     H  H  H   O CF                                                  ##STR168##     H  H  H   O N                                                   ##STR169##     H  H  H   O CCF.sub.3                                           ##STR170##     H  H  H   O CCH.sub.3                                           ##STR171##     H  H  H   O CC.sub.6 H.sub.5                                    ##STR172##     H  H  H   O CNO.sub.2                                           ##STR173##     H  H  H   O CCl                                                 ##STR174##     H  H  H   O N                                                   ##STR175##     H  H  H   O CF                                                  ##STR176##     H  H  H   O CCl                                                 ##STR177##     H  H  H   S CCl                                                 ##STR178##     H  H  H   O CH                                                  ##STR179##     H  H  H   S CBr                                                 ##STR180##     H  H  H   O CH                                                  ##STR181##     H  H  H   O CCl                                                 ##STR182##     H  H  H   O CH                                                  ##STR183##     H  H  H   O CCF.sub.3                                           ##STR184##     H  H  H   O CSCH.sub.3                                          ##STR185##     H  H  H   O CC.sub.2 H.sub.5                                    ##STR186##     H  H  H   O CCN                                                 ##STR187##     H  H  H   O CNO.sub.2                                           ##STR188##     H  H  H   O COCH.sub.3                                          ##STR189##     H  H  H   O COH                                                 ##STR190##     H  H  H   O N                                                   ##STR191##     Cl H  H   O CF                                                  ##STR192##     H  CH.sub.3                                                                          H   O CCl                                                 ##STR193##     H  H  CCH.sub.3                                                                          S CCl                                                 ##STR194##     H  H  F   O CBr                                                 ##STR195##     C.sub.2 H.sub.5                                                                   H  H   S CBr                                                 ##STR196##     H  Cl H   O COCH.sub.3                                          ##STR197##     H  H  F   O CCF.sub.3                                           ##STR198##     H  H  H   O CCl                                                 ##STR199##     H  H  H   O CF                                                  ##STR200##     H  H  H   O CH                                                  ##STR201##     H  H  H   S CCl                                                 ##STR202##     Cl H  H   O CBr                                                 ##STR203##     H  H  H   S CBr                                                 ##STR204##     H  H  H   O COCH.sub.3                                          ##STR205##     H  H  H   O CCl                                                 ##STR206##     H  H  H   O CH                                                  ##STR207##     H  H  H   O CH                                                  ##STR208##     H  H  H   O CCl                                                 ##STR209##     H  H  H   O CH                                                  ##STR210##     H  H  H   O CBr                                                 ##STR211##     H  H  H   S CBr                                                 ##STR212##     H  H  H   O COCH.sub.3                                          ##STR213##     Cl H  H   O CH                                                  ##STR214##     CH.sub.3                                                                          H  H   O CH                                                  ##STR215##     H  H  H   O CH                                                  ##STR216##     H  H  F   O CCl                                                 ##STR217##     H  H  OCH.sub.3                                                                          O CH                                                  ##STR218##     H  H  F   O CH                                                  ##STR219##     H  Cl H   O CH                                                  ##STR220##     H  CH.sub.3                                                                          H   O CH                                                  ##STR221##     H  Cl H   O CH                                                  ##STR222##     H  CH.sub.3                                                                          H   O CH                                                  ##STR223##     H  H  H   O N                                                   ##STR224##     H  H  H   O N                                                   ##STR225##     H  H  H   O N                                                   ##STR226##     H  H  H   O CCl                                                 ##STR227##     H  H  H   O CF                                                  ##STR228##     H  H  H   O CCl                                                 ##STR229##     H  H  H   O CCl                                                 ##STR230##     H  H  F   O CCl                                                 ##STR231##     H  H  OCH.sub.3                                                                          O CCl                                                 ##STR232##     H  H  H   O CBr                                                 ##STR233##     H  H  H   S CBr                                                 ##STR234##     H  H  H   O COCH.sub.3                                          ##STR235##     H  H  H   S CCl                                                 ##STR236##     H  H  H   O CCF.sub.3                                           ##STR237##     H  H  H   O CCH.sub.3                                           ##STR238##     H  H  H   O CNO.sub.2                                           ##STR239##     H  H  H   O CNH.sub.2                                           ##STR240##     H  H  H   O CCN                                                 ##STR241##     H  H  H   O CC.sub.2 H.sub.5                                    ##STR242##     H  H  H   O COH                                                 ##STR243##     H  H  H   O CSCH.sub.3                                          ##STR244##     H  H  H   O CCOOCH.sub.3                                        ##STR245##     H  H  H   O CCON(CH.sub.3).sub.2                                ##STR246##     H  H  H   O COC.sub.3 H.sub.7 (i)                               ##STR247##     H  H  H   O CC.sub.4 H.sub.9 (n)                                ##STR248##     H  H  H   O COCF.sub.2 CHF.sub.2                                ##STR249##     H  H  H   O CSC.sub.5 H.sub.11                                  ##STR250##     H  H  H   O CSOC.sub.2 H.sub.5                                  ##STR251##     H  H  H   O CSO.sub.2 CH.sub.3                                  ##STR252##     H  H  H   O                                                                                 ##STR253##                                         ##STR254##     H  H  H   O                                                                                 ##STR255##                                         ##STR256##     H  H  H   O                                                                                 ##STR257##                                         ##STR258##     H  H  H   O                                                                                 ##STR259##                                         ##STR260##     H  H  H   O                                                                                 ##STR261##                                         ##STR262##     H  H  H   O                                                                                 ##STR263##                                         ##STR264##     H  H  H   O                                                                                 ##STR265##                                         ##STR266##     H  H  H   O                                                                                 ##STR267##                                         ##STR268##     H  H  H   O CCl                                                 ##STR269##     H  H  H   O CF                                                  ##STR270##     H  H  H   O CCl                                                 ##STR271##     H  H  H   S CCl                                                 ##STR272##     H  H  H   O CBr                                                 ##STR273##     H  H  H   S CBr                                                 ##STR274##     H  H  H   O COCH.sub.3                                          ##STR275##     H  H  H   O CCl                                                __________________________________________________________________________

Formulation Examples are shown below. In the examples, the present compound (1) is shown by Compound No. in Table 3, and parts are by weight.

FORMULATION EXAMPLE 1

Fifty parts of any one of the present compounds (IV-11), (V-14) and (V-15), 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrated silicon dioxide are well mixed while being powdered to obtain a wettable powder.

FORMULATION EXAMPLE 2

Ten parts of any one of the present compounds (V-1), (V-2), (II-3), (V-4), (III-5), (III-7), (V-8), (III-9), (V-10), (IV-11), (V-14), (V-15), (V-16), (V-17), (V-18), (V-19), (V-20), (V-21), (V-22) and (V-23). 14 parts of polyoxyethvlene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 40 parts of xylene and 30 parts of cyclohexanone are well mixed to obtain an emulsifiable concentrate.

FORMULATION EXAMPLE 3

Two parts of any one of the present compounds (IV-11), (V-14) and (V-15), 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignosulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed. The resulting mixture is well kneaded with water, granulated and dried to obtain a granule.

FORMULATION EXAMPLE 4

Twenty five parts of any one of the present compounds (V-1), (V-2), (II-3), (V-4), (III-5), (III-7), (V-8), (III-9), (V-10), (IV-11), (V-14), (V-15), (V-16), (V-17), (V-18), (V-19), (V-20), (V-21), (V-22) and (V-23), 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed and wetpulverized until the particle size decreases to 5 microns or less. Thus, a suspension formulation is obtained.

That the present compounds are useful as an active ingredient for herbicides is shown by the following test examples. In the examples, the present compound (1) is shown by Compound No. in Table 1, and compounds used for comparison are shown by Compound symbol in Table 3.

                                      TABLE 3                                      __________________________________________________________________________     Compound                                                                       symbol                                                                               Structural formula   Remarks                                             __________________________________________________________________________            ##STR276##          EP-0 249 708-Al (n.sub.D.sup.23 1.5271)             B                                                                                     ##STR277##          EP-0 249 708-Al (Compound No. 1)                    C                                                                                     ##STR278##          EP-0 223 406-Al (Compound No. 16)                   D                                                                                     ##STR279##          EP-0 223 406-Al (Compound No. 18)                   E                                                                                     ##STR280##          EP-0 223 406-Al (Compound No. 20)                   F                                                                                     ##STR281##          EP-0 249 707-Al (Compound No. 4)                    G                                                                                     ##STR282##          EP-0 249 707-Al (Compound No. 1)                    H                                                                                     ##STR283##          Ep-0 249 707-Al (Compound No. 8)                    J                                                                                     ##STR284##          Comparative Compound (n.sub.D.sup.24                __________________________________________________________________________                                1.5129)                                        

The determination of the herbicidal activity and phytotoxicity was carried out as follows: When the states of emergence and growth of treated test plants (weeds and crops) at the time of determination were completely the same as or hardly different from those of untreated test plants, the value of determination was taken as "0". When the treated test plants were completely killed, or their emergence and growth were completely inhibited, the value of determination was taken as "5", and an interval between "0" and "5" was divided into four stages, i.e. "1", "2", "3" and "4". The evaluation was thus made in six stages.

TEST EXAMPLE 1 Soil surface treatment test in upland field soil

Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and seeds of Japanese millet, oats, tall morningglory and velvetleaf were sowed in the respective pots and covered with soil. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 4.

                  TABLE 4                                                          ______________________________________                                         Dosage rate    Herbicidal activity                                                     of active                Tall                                          Test    ingredient Japanese      morning-                                                                              Velvet-                                compound                                                                               (g/a)      millet   Oats glory  leaf                                   ______________________________________                                         (V-1)   5          5        5    4      4                                              1.25       5        5    3      4                                      (V-2)   5          5        4    3      4                                              1.25       5        4    3      4                                      (II-3)  5          5        4    3      4                                      (V-4)   5          5        4    3      4                                              1.25       5        4    3      3                                      (III-5) 5          5        4    3      4                                              1.25       5        4    3      4                                      (III-7) 5          5        4    4      4                                              1.25       5        4    3      4                                      (V-8)   5          5        5    4      5                                              1.25       5        4    3      4                                      (III-9) 5          5        4    3      4                                              1.25       5        4    3      4                                      (V-10)  5          5        4    4      4                                              1.25       5        4    3      3                                      (IV-11) 5          5        5    4      4                                              1.25       5        4    4      4                                      A       5          4        3    0      1                                              1.25       2        1    0      0                                      B       5          4        3    0      2                                              1.25       2        1    0      0                                      C       5          3        3    0      1                                              1.25       1        2    0      0                                      ______________________________________                                    

TEST EXAMPLE 2 Soil surface treatment test in upland field soil

Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and seeds of velvetleaf were sowed in the respective pots and covered with soil. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 5.

                  TABLE 5                                                          ______________________________________                                         Test       Dosage rate of Herbicidal activity                                  compound   active ingredient (g/a)                                                                       Velvetleaf                                           ______________________________________                                         (V-17)     5              4                                                    A          5              1                                                    ______________________________________                                    

TEST EXAMPLE 3 Soil surface treatment test in upland field soil

Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and seeds of Japanese millet, oats and velvetleaf were sowed in the respective pots and covered with soil. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 6.

                  TABLE 6                                                          ______________________________________                                                Dosage rate of                                                                            Herbicidal activity                                          Test     active ingredient                                                                           Japanese       Velvet-                                   compound (g/a)        millet    Oats leaf                                      ______________________________________                                         (V-19)   5            4         4    3                                         (V-20)   5            4         4    4                                         (V-21)   5            4         4    4                                         (V-22)   5            5         4    4                                         (V-23)   5            4         3    3                                         H        5            2         1    3                                         ______________________________________                                    

TEST EXAMPLE 4 Soil surface treatment test in upland field soil

Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and seeds of Japanese millet were sowed in the respective pots and covered with soil. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 7.

                  TABLE 7                                                          ______________________________________                                         Test       Dosage rate of Herbicidal activity                                  compound   active ingredient (g/a)                                                                       Japanese millet                                      ______________________________________                                         (III-7)    0.31           4                                                    (V-10)     0.31           4                                                    D          0.31           3                                                    E          0.31           1                                                    F          0.31           2                                                    ______________________________________                                    

TEST EXAMPLE 5 Foliar treatment test in upland field soil

Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and seeds of Japanese millet, oats, radish, velvetleaf and tall morningglory were sowed in the respective pots and cultivated for 8 days in a greenhouse.

Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with a spreading agent-containing water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined.

The results are shown in Table 8.

                  TABLE 8                                                          ______________________________________                                         Dosage                                                                         rate of     Herbicidal activity                                                Test  active                              Tall                                 com-  ingredient                                                                               Japanese            Velvet                                                                               morning-                             pound (g/a)     millet   Oats Radish                                                                               leaf  glory                                ______________________________________                                         (V-1) 5         5        5    4     5     4                                    (V-2) 5         5        4    4     5     4                                    (II-3)                                                                               5         4        5    4     3     3                                    (V-4) 5         5        4    4     5     5                                    (III-5)                                                                              5         4        4    3     5     3                                    (III-7)                                                                              5         5        4    4     4     4                                    (V-8) 5         5        5    4     5     4                                    (III-9)                                                                              5         5        4    4     4     4                                    (V-10)                                                                               5         5        5    4     5     4                                    (IV-11)                                                                              5         4        4    3     4     3                                    A     5         4        2    1     1     2                                    B     5         3        3    1     1     1                                    C     5         3        2    2     1     2                                    ______________________________________                                    

TEST EXAMPLE 6 Foliar treatment test in upland field soil

Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and seeds of Japanese millet, oats, radish and velvetleaf were sowed in the respective pots and cultivated for 8 days in a greenhouse.

Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with a spreading agent-containing water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined.

The results are shown in Table 9.

                  TABLE 9                                                          ______________________________________                                         Dosage          Herbicidal activity                                            Test    rate of active                                                                             Japanese            Velvet-                                compound                                                                               ingredient (g/a)                                                                           millet   Oats Radish                                                                               leaf                                   ______________________________________                                         (V-19)  5           4        4    3     4                                      (V-20)  5           5        5    5     5                                      (V-21)  5           5        5    5     5                                      (V-22)  5           5        5    5     5                                      (V-23)  5           4        3    5     5                                      E       5           2        2    2     2                                      ______________________________________                                    

TEST EXAMPLE 7 Foliar treatment test in upland field soil

Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and seeds of Japanese millet, oats and radish were sowed in the respective pots and cultivated for 8 days in a greenhouse.

Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with a spreading agent-containing water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined.

The results are shown in Table 10.

                  TABLE 10                                                         ______________________________________                                                Dosage rate of                                                                            Herbicidal activity                                          Test     active ingredient                                                                           Japanese                                                 compound (g/a)        millet    Oats  Radish                                   ______________________________________                                         (V-20)   0.31         4         4     4                                        (V-21)   0.31         4         4     4                                        (V-22)   0.31         4         4     4                                        F        0.31         1         1     1                                        J        0.31         2         2     2                                        ______________________________________                                    

TEST EXAMPLE 8 Foliar treatment test in upland field soil

Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and seeds of Japanese millet were sowed in the respective pots and cultivated for 8 days in a greenhouse.

Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with a spreading agent-containing water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined.

The results are shown in Table 11.

                  TABLE 11                                                         ______________________________________                                         Test       Dosage rate of Herbicidal activity                                  compound   active ingredient (g/a)                                                                       Japanese millet                                      ______________________________________                                         (V-10)     0.08           4                                                    D          0.08           2                                                    G          0.08           2                                                    ______________________________________                                    

TEST EXAMPLE 9 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of soybean, cotton, corn, velvetleaf, black nightshade, barnyardgrass, giant foxtail and johnsongrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer.

After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 12.

                                      TABLE 12                                     __________________________________________________________________________     Dosage rate   Phytotoxicity                                                                            Herbicidal activity                                    Test  of active                                                                              Soy-      Velvet-                                                                             Black Barnyard-                                                                            Green                                                                              Johnson-                          compound                                                                             ingredient (g/a)                                                                       bean                                                                              Cotton                                                                             Co2n                                                                              leaf nights(ade                                                                           grass foxtail                                                                            grass                             __________________________________________________________________________     (V-1) 5       1  0   1  4    5     5     5   4                                       1.25    1  0   0  3    5     4     4   4                                 (II-3)                                                                               5       0  0   0  4    4     4     4   4                                       1.25    0  0   0  3    4     3     3   3                                 (III-5)                                                                              5       0  0   1  3    4     4     4   4                                 (III-7)                                                                              5       1  1   1  3    4     4     4   5                                 (V-8) 5       1  1   1  4    5     5     4   4                                 (III-9)                                                                              5       0  1   1  3    4     4     4   4                                 A     5       2  2   0  0    0     2     1   3                                       1.25    0  2   0  0    0     1     0   2                                 C     5       0  0   0  0    0     1     1   0                                       1.25    0  0   0  0    0     1     1   0                                 H     5       0  0   0  2    2     0     1   0                                 __________________________________________________________________________

TEST EXAMPLE 10 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of cotton, black nightshade and sicklepod were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer.

After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 13.

                  TABLE 13                                                         ______________________________________                                         Dosage          Phyto-   Herbicidal actiity                                    Test    rate of active                                                                             toxicity Black                                             compound                                                                               ingredient (g/a)                                                                           Cotton   nightshade                                                                             Sicklepod                                 ______________________________________                                         (V-23)  5           0        5       4                                         D       5           3        4       0                                         H       5           0        2       1                                         ______________________________________                                    

TEST EXAMPLE 11 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of soybean, cotton, corn, back nightshade and johnsongrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer.

After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 14.

                  TABLE 14                                                         ______________________________________                                               Dosage                                                                         rate                                                                     Test  of active Phytotoxicity Herbicidal activity                              com-  ingredient                                                                               Soy-              Black   Johnson-                             pound (g/a)     bean   Cotton                                                                               Corn nightshade                                                                             grass                                ______________________________________                                         (V-21)                                                                               2.5       0      1     0    4       4                                    A     2.5       1      2     0    0       3                                    B     2.5       0      0     0    0       2                                    C     2.5       0      0     0    0       0                                    ______________________________________                                    

TEST EXAMPLE 12 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of cotton, back nightshade, barnyardgrass, giant foxtail and johnsongrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer.

After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 15.

                  TABLE 15                                                         ______________________________________                                         Dosage                                                                         rate                Herbicidal activity                                        Test  of active Phyto-  Black Barn-                                            com-  ingredient                                                                               toxicity                                                                               night-                                                                               yard- Giant Johnson-                             pound (g/a)     Cotton  shade grass foxtail                                                                              grass                                ______________________________________                                         (V-4) 5         0       4     4     4     4                                    (IV-11)                                                                              5         0       4     4     4     4                                    A     5         2       0     2     1     3                                    C     5         0       0     1     1     0                                    ______________________________________                                    

TEST EXAMPLE 13 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of soybean, black nightshade and giant foxtail were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsified concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer.

After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 16.

                  TABLE 16                                                         ______________________________________                                         Dosage           Phyto-   Herbicidal activity                                  Test    rate of active                                                                              toxicity Black    Giant                                   compound                                                                               ingredient (g/a)                                                                            Soybean  nightshade                                                                              foxtail                                 ______________________________________                                         (V-2)   5            1        4        5                                       (V-10)  5            1        4        4                                       (V-18)  5            0        4        3                                       (V-19)  5            0        4        3                                       (V-20)  5            1        4        3                                       (V-21)  5            0        4        4                                       (V-22)  5            1        4        4                                       B       5            0        0        3                                       H       5            0        2        1                                       ______________________________________                                    

TEST EXAMPLE 15 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of soybean, barnyardgrass, giant foxtail and johnsongrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer.

After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 17.

                  TABLE 17                                                         ______________________________________                                               Dosage                                                                         rate of                                                                  Test  active     Phyto-   Herbicidal activity                                  com-  ingredient toxicity Barnyard-                                                                              Giant Johnson-                               pound (g/a)      Soybean  grass   foxtail                                                                              grass                                  ______________________________________                                         (IV-11)                                                                              2.5        0        3       4     3                                      F     2.5        1        0       2     2                                      ______________________________________                                    

TEST EXAMPLE 15 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of corn, black nightshade and giant foxtail were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer.

After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 18.

                  TABLE 18                                                         ______________________________________                                                          Phyto-                                                                               Herbicidal activity                                     Test    Dosage rate of toxicity                                                                               Black   Giant                                   compound                                                                               active ingredient (g/a)                                                                       Corn    nightshade                                                                             foxtail                                 ______________________________________                                         (V-22)  5              0       4       4                                       A       5              0       0       1                                       ______________________________________                                    

TEST EXAMPLE 16 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of soybean, cotton, corn, giant foxtail and johnsongrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer.

After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 19.

                  TABLE 19                                                         ______________________________________                                                                         Herbicidal                                     Test  Dosage rate Phytotoxicity activity                                       com-  of active   Soy-              Giant Johnson-                             pound ingredient (g/a)                                                                           bean   Cotton                                                                               Corn foxtail                                                                              grass                                ______________________________________                                         (V-1) 0.63        0      0     0    4     4                                    E     0.63        0      0     0    2     2                                    ______________________________________                                    

TEST EXAMPLE 17 Foliar treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of cotton, corn, tall morningglory, velvetleaf, black nightshade, sicklepod, barnyardgrass, giant foxtail and johsongrass were sowed in the respective vats and cultivated for 16 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. The conditions of growth of the weeds and crops at that time varied depending upon the kind of the test plants, but the test plants were in the 0.5- to 4-leaf stage and were 5 to 30 cm in height. Eighteen days after application, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 20. This test was carried out in a greenhouse through the whole test period.

                                      TABLE 20                                     __________________________________________________________________________     Dosage rate           Herbicidal activity                                      Test  of active                                                                              Phytotoxicity                                                                          Tall    Velvet-                                                                             Black       Barnyard-                                                                            Giant                                                                               Johnson-             compound                                                                             ingredient (g/a)                                                                       Cotton                                                                             Corn                                                                               morning-glory                                                                          leaf nightshade                                                                           Sicklepod                                                                            grass foxtail                                                                             grass                __________________________________________________________________________     (V-1) 1.25    1   0   4       5    5     4     4     4    4                          0.31    1   0   4       4    5     3     4     4    4                    (V-2) 0.31    1   1   3       4    5     4     3     4    4                    (III-5)                                                                              1.25    1   0   4       5    5     5     4     4    4                    (III-7)                                                                              1.25    1   1   3       4    5     3     5     3    5                    (III-9)                                                                              1.25    1   0   4       4    4     4     4     4    5                          0.31    1   0   4       4    4     3     4     4    5                    (V-10)                                                                               1.25    1   1   3       5    5     4     4     5    5                    A     1.25    0   0   0       0    4     1     2     0    2                          0.31    0   0   0       0    3     0     1     0    0                    B     1.25    0   0   0       1    3     2     1     0    1                          0.31    0   0   0       1    3     1     0     0    0                    D     1.25    2   2   0       1    2     0     2     0    3                          0.31    1   0   0       0    2     0     2     0    3                    __________________________________________________________________________

TEST EXAMPLE 18 Foliar treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of cotton, tall morningglory, sicklepod, giant foxtail and johnsongrass were sowed in the respective vats and cultivated for 16 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. The conditions of growth of the weeds and crop at that time varied depending upon the kind of the test plants, but the test plants were in the 0.5- to 2.5-leaf stage and were 5 to 15 cm in height. Eighteen days after application, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 21. This test was carried out in a greenhouse through the whole test period.

                  TABLE 21                                                         ______________________________________                                         Dosage                                                                         rate of            Herbicidal activity                                         Test  active in-                                                                              Phyto-  Tall                                                    com-  gredient toxicity                                                                               morning-                                                                              Sickle-                                                                              Giant Johnson-                             pound (g/a)    Cotton  glory  pod   foxtail                                                                              grass                                ______________________________________                                         (V-1) 1.25     1       4      4     4     4                                    (III-9)                                                                              1.25     1       4      4     4     5                                    F     1.25     2       3      3     1     3                                    ______________________________________                                    

TEST EXAMPLE 19 Foliar treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of velvetleaf, barnyardgrass, giant foxtail and johnsongrass were sowed in the respective vats and cultivated for 16 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. The conditions of growth of the weeds at that time varied depending upon the kind of the test plants, but the test plants were in the 1- to 2.5-leaf stage and were 5 to 15 cm in height. Eighteen days after application, the herbicidal activity was examined. The results are shown in Table 22. This test was carried out in a greenhouse through the whole test period.

                  TABLE 22                                                         ______________________________________                                               Dosage rate                                                              Test  of active  Herbicidal activity                                           com-  ingredient Velvet-  Barnyard-                                                                              Giant Johnson-                               pound (g/a)      leaf     grass   foxtail                                                                              grass                                  ______________________________________                                         (II-3)                                                                               5          5        5       5     5                                      A     5          0        2       0     2                                      ______________________________________                                    

TEST EXAMPLE 20 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of wheat, pale smartweed, cleavers, chickweed, birdseye speedwell, field pansy, downy brome, wild oat, blackgrass and annual bluegrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 25 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 23.

                                      TABLE 23                                     __________________________________________________________________________     Dosage           Phyto-                                                                             Herbicidal activity                                       Test  rate of active                                                                            toxicity                                                                           Pale       Chick-                                                                             Birdseye                                                                             Field                                                                              Downy                                                                              Wild                                                                               Black-                                                                             Annual               compound                                                                             ingredient (g/a)                                                                          Wheat                                                                              smartweed                                                                            Cleavers                                                                            weed                                                                               speedwell                                                                            pansy                                                                              brome                                                                              oat grass                                                                              bluegrass            __________________________________________________________________________     (V-4) 5          0   4     5    4   4     3   4   4   4   4                          1.25       0   4     3    3   4     3   4   3   4   4                    (III-9)                                                                              5          0   4     3    4   4     4   5   4   4   4                          1.25       0   4     3    3   4     3   4   4   3   4                    (IV-11)                                                                              5          0   4     3    4   5     4   5   4   4   4                          1.25       0   4     3    3   5     3   5   4   3   4                    A     5          3   2     2    0   3     0   0   2   3   3                          1.25       1   0     0    0   0     0   0   0   2   3                    B     5          4   4     3    4   4     3   0   4   4   3                          1.25       1   2     3    3   3     0   0   2   2   3                    C     5          1   0     1    1   2     1   2   3   3   3                          1.25       0   0     0    0   1     0   0   1   1   2                    __________________________________________________________________________

TEST EXAMPLE 21 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of beet, pale smartweed, downy brome and annual bluegrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 25 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 24.

                  TABLE 24                                                         ______________________________________                                         Test  Dosage      Phyto-  Herbicidal activity                                  com-  rate of active                                                                             toxicity                                                                               Pale    Downy Annual                                 pound ingredient (g/a)                                                                           Beet    smartweed                                                                              brome bluegrass                              ______________________________________                                         (IV-11)                                                                              1.25        1       4       5     4                                      (V-22)                                                                               0.63        1       4       4     4                                      H     2.5         3       1       2     3                                      ______________________________________                                    

TEST EXAMPLE 22 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of wheat and annual bluegrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 25 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 25.

                  TABLE 25                                                         ______________________________________                                                 Dosage                                                                 Test    rate of active                                                                             Phytotoxicity                                                                             Herbicidal activity                             compound                                                                               ingredient (g/a)                                                                           Wheat      Annual bluegrass                                ______________________________________                                         (V-2)   0.31        0          4                                               (III-7) 0.31        0          4                                               (V-8)   0.31        0          4                                               G       0.31        2          0                                               ______________________________________                                    

TEST EXAMPLE 23 Soil treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of wheat, birdseye speedwell, downy brome and annular bluegrass were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied onto the whole soil surface by means of an automatic sprayer. After application, the test plants were cultivated for 25 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 26.

                  TABLE 26                                                         ______________________________________                                         Test  Dosage      Phyto-  Herbicidal activity                                  com-  rate of active                                                                             toxicity                                                                               Birdseye                                                                               Downy Annual                                 pound ingredient (g/a)                                                                           Wheat   speedwell                                                                              brome bluegrass                              ______________________________________                                         (III-5)                                                                              1.25        0       4       4     4                                      (V-8) 1.25        0       4       4     4                                      (V-10)                                                                               1.25        0       4       4     4                                      (V-19)                                                                               2.5         0       4       4     4                                      B     5           4       4       0     3                                            1.25        1       3       0     3                                      ______________________________________                                    

TEST EXAMPLE 24 Foliar treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of pale smartweed, cleavers, chickweed, birdseye speedwell, field pansy, downy brome, wild oat, blackgrass and annual bluegrass were sowed in the respective vats and cultivated for 31 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. The conditions of growth of the weeds at that time varied depending upon the kind of the test plants, but the test plants were in the 1- to 4-leaf stage and were 3 to 25 cm in height. Twenty-five days after application, the herbicidal activity was examined. The results are shown in Table 27. This test was carried out in a greenhouse through the whole test period.

                                      TABLE 27                                     __________________________________________________________________________     Test                                                                               Dosage     Herbicidal activity                                             com-                                                                               rate of active                                                                            Pale       Chick-                                                                             Birdseye                                                                             Field                                                                              Downy                                                                              Wild                                                                              Black-                                                                             Annual                      pound                                                                              ingredient (g/a)                                                                          smartweed                                                                            Cleavers                                                                            weed                                                                               speedwell                                                                            pansy                                                                              brome                                                                              oat                                                                               grass                                                                              bluegrass                   __________________________________________________________________________     (V-1)                                                                              2.5        5     4    4   5     5   4   4  5   5                           (V-4)                                                                              2.5        4     4    3   4     4   4   3  4   4                           (V-8)                                                                              2.5        5     4    3   4     4   4   4  4   4                           (III-9)                                                                            2.5        4     4    4   4     3   4   4  4   4                           A   2.5        2     3    1   3     0   3   3  3   3                           B   2.5        3     0    1   3     0   3   3  3   2                           C   2.5        0     1    1   0     0   0   0  1   0                           __________________________________________________________________________

TEST EXAMPLE 25 Foliar treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of pale smartweed, chickweed, birdseye speedwell, field pansy, downy brome, wild oat, blackgrass and annual bluegrass were sowed in the respective vats and cultivated for 31 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. The conditions of growth of the weeds at that time varied depending upon the kind of the test plants, but the test plants were in the 1- to 4-leaf stage and were 3 to 25 cm in height. Twenty-five days after application, the herbicidal activity was examined. The results are shown in Table 28. This test was carried out in a greenhouse through the whole test period.

                                      TABLE 28                                     __________________________________________________________________________                      Herbicidal activity                                           Test  Dosage rate of active                                                                     Pale        Birdseye                                                                             Field                                                                              Downy                                                                              Wild     Annual                     compound                                                                             ingredient (g/a)                                                                          smartweed                                                                            Chickweed                                                                            speedwell                                                                            pansy                                                                              brome                                                                              oat                                                                               Blackgrass                                                                           bluegrass                  __________________________________________________________________________     (V-21)                                                                               0.16       5     5     4     5   4   4  4     4                          (V-22)                                                                               0.16       4     5     5     5   4   4  4     3                          F     0.16       3     3     3     3   0   1  1     2                          J     0.16       1     0     2     2   2   1  1     2                          __________________________________________________________________________

TEST EXAMPLE 26 Foliar treatment test in upland field soil

Vats of 33×23 cm² in area and 11 cm in depth were filled with upland field soil, and seeds of wheat, pale smartweed, cleavers, downy brome and annual bluegrass were sowed in the respective vats and cultivated for 31 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water corresponding to 10 liters/are and uniformly applied from above onto the whole foliar portion of the test plants by means of an automatic sprayer. The conditions of growth of the weeds and crop at that time varied depending upon the kind of the test plants, but the test plants were in the 2- to 4-leaf stage and were 5 to 25 cm in height. Twenty-five days after application, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 29. This test was carried out in a greenhouse through the whole test period.

                  TABLE 29                                                         ______________________________________                                         Dosage               Herbicidal activity                                       Test  rate of active                                                                            Phyto-  Pale              Annual                              com-  ingredient toxicity                                                                               smart-                                                                               Clea- Downy blue-                               pound (g/a)      Wheat   weed  vers  brome grass                               ______________________________________                                         (V-1) 0.31       1       4     4     4     4                                   (V-4) 0.63       1       4     3     4     4                                   H     0.63       2       3     1     1     2                                   J     0.63       2       3     3     3     2                                   ______________________________________                                    

TEST EXAMPLE 27 Flooding treatment test in paddy field

Cylindrical plastic pots of 8 cm in diameter and 12 cm in depth were filled with paddy field soil, and seeds of barnyardgrass and bulrush were sowed 1 to 2 cm deep under the soil surface. After creating a state of paddy field by flooding, a tuber of arrowhead was buried 1 to 2 cm deep under the soil surface and cultivated in a greenhouse. After 6 days (at the initial stage of generation of every weed), the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with 2.5 ml of water and applied onto the water surface. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 30.

                  TABLE 30                                                         ______________________________________                                         Dosage           Herbicidal activity                                           Test    rate of active                                                                              Barnyard                                                  compound                                                                               ingredient (g/a)                                                                            grass    Bulrush                                                                               Arrowhead                                 ______________________________________                                         (V-1)   0.63         5        5      3                                         (V-2)   0.63         5        3      4                                         (I-6)   0.63         5        3      3                                         (V-8)   0.63         4        3      4                                         (III-9) 0.63         4        4      4                                         (V-10)  0.63         4        3      4                                         (IV-11) 0.63         5        3      3                                         A       0.63         4        1      3                                         B       0.63         2        0      3                                         C       0.63         3        0      3                                         E       0.63         1        0      1                                         F       0.63         2        2      2                                         G       0.63         2        1      2                                         ______________________________________                                    

TEST EXAMPLE 28 Flooding treatment test in paddy field

Wager's pots of 200 cm² were filled with paddy field soil, and seeds of barnyardgrass and broadleaf weeds (i.e. false pimpernel, indian toothcup, water wort and red stem [Ammannia spp.]) were sowed 1 to 2 cm deep under the soil surface. After creating a state of paddy field by water flooding, tubers of arrowhead and water nutgrass were buried 1 to 2 cm deep under the soil surface. Also rice seedlings of 2-leaf stage were transplanted into the pots. The weeds and crops were cultivated in a greenhouse. After 4 days (at the initial stage of germination of barnyardgrass), the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, a prescribed amount of each of the emulsifiable concentrates was diluted with 10 of water and applied onto the water surface in the pots. Water leakage decresing the depth of flooding water by 3 cm was carried out on the day subsequent to and two days after the application of test compounds. The depth of flooding water in each pot was recovered and kept at 4 cm, while the test plants were cultivated for 20 days in a greenhouse. Then, the herbicidal activity and phytotoxicity was examined. The results are shown in Table 31.

                  TABLE 31                                                         ______________________________________                                         Dosage                                                                         rate of             Herbicidal activity                                        Test  active    Phyto-  Barn- Broad-       Water                               com-  ingredient                                                                               toxicity                                                                               yard  leaf  Arrow- nut-                                pound (g/a)     Rice    grass weeds head   grass                               ______________________________________                                         (V-4) 0.16      0       4     4     4      4                                   (III-7)                                                                              0.16      0       3     5     3      3                                   A     0.16      0       0     0     1      0                                   B     0.16      0       0     0     0      0                                   C     0.16      0       0     0     0      0                                   ______________________________________                                    

TEST EXAMPLE 29 Flooding treatment test in paddy field

Wager's pots of 200 cm² were filled with paddy field soil, and seeds of barnyardgrass and broadleaf weeds (i.e. false pimpernel, indian toothcup, water wort and red stem [Ammannia spp.]) were sowed 1 to 2 cm deep under the soil surface. After creating a state of paddy field by water flooding, tubers of arrowhead and water nutgrass were buried 1 to 2 cm deep under the soil surface. The weeds were cultivated in a greenhouse. After 11 days (at the 2-leaf stage of barnyardgrass), the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, a prescribed amount of each of the emulsifiable concentrates was diluted with 10 ml of water and applied onto the water surface in the pots. Water leakage decreasing the depth of flooding water by 3 cm was carried out on the day subsequent to and two days after the application of test compounds. The depth of flooding water in each pot was recovered and kept at 4 cm, while the test plants were cultivated for 20 days in a greenhouse. Then, the herbicidal activity was examined. The results are shown in Table 32.

                  TABLE 32                                                         ______________________________________                                               Dosage                                                                         rate of                                                                  Test  active    Herbicidal activity                                            com-  ingredient                                                                               Barnyard Broadleaf                                                                              Arrow- Water                                  pound (g/a)     grass    weeds   head   nutgrass                               ______________________________________                                         (V-1) 0.63      4        3       3      4                                      (V-4) 0.63      5        4       4      3                                      (III-7)                                                                              0.63      4        4       3      3                                      (III-9)                                                                              0.63      4        3       4      3                                      A     0.63      1        0       2      0                                      C     0.63      0        0       0      0                                      ______________________________________                                    

TEST EXAMPLE 30 Flooding treatment test in paddy field

Wager's pots of 200 cm² were filled with paddy field soil, and seeds of barnyardgrass and broadleaf weeds (i.e. false pimpernel, indian toothcup, water wort and red stem [Ammannia spp.]) were sowed 1 to 2 cm deep under the soil surface. After creating the state of paddy field by water flooding, tubers of arrowhead were buried 1 to 2 cm deep under the soil surface. Also rice seedlings of 2-leaf stage were transplanted into the pots. The weeds and crop were cultivated in a greenhouse. After 11 days (at the 2-leaf stage of barnyardgrass), the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, a prescribed amount of each of the emulsifiable concentrates was diluted with 10 ml of water and applied onto the water surface in the pots. Water leakage decresing the depth of flooding water by 3 cm was carried out on the day subsequent to and two days after the application of test compounds. The depth of flooding water in each pot was recovered and kept at 4 cm, while the test plants were cultivated for 20 days in a greenhouse. Then, the herbicidal activity and phytotoxicity was examined. The results are shown in Table 33.

                  TABLE 33                                                         ______________________________________                                               Dosage                                                                   Test  rate of active                                                                            Phyto-  Herbicidal activity                                   com-  ingredient toxicity                                                                               Barnyard                                                                              Broadleaf                                                                              Arrow-                                 pound (g/a)      Rice    grass  weeds   head                                   ______________________________________                                         (V-4) 0.31       1       5      4       4                                      (III-7)                                                                              0.31       0       4      4       3                                      (III-9)                                                                              0.31       1       4      3       4                                      A     0.31       0       0      0       2                                      J     0.31       0       1      0       0                                      ______________________________________                                     

What is claimed is:
 1. A compound having the formula, ##STR285## wherein A is a 5-7 membered saturated aliphatic hetero ring containing as the sole hetero atoms two non-adjacent oxygen atoms, which may be substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl and halogen, or C₁ -C₆ alkyl having a 5-7 membered saturated aliphatic hetero ring containing as the sole hetero atoms two non-adjacent oxygen atoms, which may be substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl and halogen;X is oxygen or sulfur; Z is CY⁴ ; each of Y¹, Y² and Y³, which may be the same or different, is hydrogen, halogen, C₁ -C₆ alkyl or C₁ -C₆ alkoxy; and Y⁴ is hydrogen, hydroxyl, nitro, halogen, C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, --CON(C₁ -C₆ alkyl)(C₁ -C₆ alkyl), --NH₂, --S(=O)_(m) --C₁ -C₆ alkyl (m=0, 1 or 2), halo C₁ -C₆ alkoxy, cyano, C₁ -C₆ alkoxycarbonyl, phenyl, phenyl substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen.
 2. A compound according to claim 1, wherein A is C₁ -C₆ alkyl having a 5-7 membered saturated aliphatic hetero ring containing as the sole hetero atoms two non-adjacent oxygen atoms.
 3. A compound according to claim 2, wherein A is (1,3-dioxolane-2-yl) C₁ -C₆ alkyl or (1,3-dioxan-2-yl) C₁ -C₆ alkyl.
 4. A compound according to claim 3, wherein A is (1,3-dioxolane-2-yl)ethyl or (1,3-dioxan-2yl)ethyl.
 5. A compound according to claim 1, wherein X is oxygen.
 6. A compound according to claim 1, wherein Z is CY⁴ wherein Y⁴ is hydrogen, halogen, halo C₁ -C₆ alkyl, C₁ -C₆ alkyl, C₁ -C₆ alkoxy, phenyl or phenyl substituted with at least one member selected from the group consisting of C₁ -C₆ alkyl, C₁ -C₆ alkoxy, halo C₁ -C₆ alkyl, C₁ -C₆ alkoxycarbonyl and halogen.
 7. A compound according to claim 3, wherein Z is CH, CF, CCl, CBr or CI.
 8. A compound according to claim 1, wherein Z is CF, CCl, CBr or CI.
 9. A compound according to claim 1, wherein both Y¹ and Y² are hydrogen or fluorine, and Y³ is hydrogen, fluorine or C₁ -C₆ alkoxy.
 10. Compound according to claim 1 which is ##STR286## 